Iminoboronate Polymers as Dynamically Adaptable, Photoactive Materials
Lead Research Organisation:
University of Cambridge
Department Name: Chemistry
Abstract
Polymers incorporating dynamic covalent bonds form a class of "smart" materials that are able to adapt to-or can be altered in response to-applied chemical or environmental stimuli. We propose a new class of dynamic, conjugated polymers based on the reversible iminoboronate ester bonding motif. Simple AB-type monomers incorporating aldehyde, amine, and boronic acid functionalities will polymerize together with diols to produce iminoboronate ester polymers. The presence of orthogonal dynamic imine and boronate ester bonds will allow us to develop easily functionalizable, and thus tuneable, multicomponent polymer materials that possess the ability to reorganise or adapt in response to various external stimuli. By incorporating electronically distinct diols, the photophysical properties of the conjugated polyimine polymer backbone may be tuned, providing a predictable pathway for attaining desired material properties. The unique set of characteristics of this materials system - highly tuneable electronic properties, structural rigidity through dative N-B stabilisation and electrochemical stability due to non-conjugated boron functionalization - promise to make these polymers strong candidates for light-emitting devices. (Additionally, obtaining a fundamental understanding of the affinity of the iminoboronate for electronically different diols will allow us to promote consecutive changes in polymer properties through successive diol exchanges.) These materials will be investigated as fluorescent polyreceptors for specific diols and as controllably crosslinkable or decrosslinkable materials with the addition or displacement of tetrols. Development of these high-value smart materials will lay the groundwork for the next generation of multifunctional devices, such as blue-light-emitting polymers with superior efficiency and electrochemical stability to the state-of-the-art poly(fluorene) OLEDs.
Planned Impact
Beyond the academic community, the development of new polymer materials and devices in this project will have impact on industry and the general public.
Industry: A key goal of this project is the production of new polymeric luminescent materials that are capable of emitting efficiently at a tuneable wavelength. In particular, the impact of a new family of materials for blue LEDs is very considerable, in the near term for use in full colour displays in phones, tablets and TVs, and in the longer term for OLED lighting. This is directly relevant to the very strong materials chemistry industrial activities in the UK, including CDT-Sumitomo in Cambridge and Merck in Southampton. These companies have developed state-of-the-art materials sets that are now used by Asian display manufacturers. For example, the 4k-resolution 55-inch OLED TV demonstrated by Panasonic is fabricated by printing of materials sets developed by CDT-Sumitomo. This falls very directly within the scope of 'Advanced Materials', one of the UK's 'Eight Great Technologies'.
Intellectual property (IP) will be protected and exploited in accordance with the published policy of the University of Cambridge to the benefit of all individuals and institutions involved. After the protection of any relevant IP, dissemination will be through publication in top international journals and domestic and international presentations. We will make sure that relevant IP is patented, potential licensees are recognised, and that possibilities for launching spin-outs are also properly identified.
General public: Appreciation and public support for scientific progress have underpinned technological progress in the UK ever since the practice of science became professionalised in the 19th century. We are committed to maintaining our side of this dialogue through explaining to the public what we do and why. One mechanism for this is press coverage of our research programme. The Nitschke group's 2009 Science paper generated a dozen stories in newspapers, TV, and radio across more than five countries, all with a positive bent. Another mechanism is structured outreach events; JRN will present his group's research to the 2014 international 'Pint of Science' festival (http://www.pintofscience.com/).
Education: In the context of undergraduate education, one of the Nitschke group's self-assembled systems will be highlighted in the next edition of a first-year undergraduate chemistry textbook and has already been adapted for use in undergraduate practical exercises.
Industry: A key goal of this project is the production of new polymeric luminescent materials that are capable of emitting efficiently at a tuneable wavelength. In particular, the impact of a new family of materials for blue LEDs is very considerable, in the near term for use in full colour displays in phones, tablets and TVs, and in the longer term for OLED lighting. This is directly relevant to the very strong materials chemistry industrial activities in the UK, including CDT-Sumitomo in Cambridge and Merck in Southampton. These companies have developed state-of-the-art materials sets that are now used by Asian display manufacturers. For example, the 4k-resolution 55-inch OLED TV demonstrated by Panasonic is fabricated by printing of materials sets developed by CDT-Sumitomo. This falls very directly within the scope of 'Advanced Materials', one of the UK's 'Eight Great Technologies'.
Intellectual property (IP) will be protected and exploited in accordance with the published policy of the University of Cambridge to the benefit of all individuals and institutions involved. After the protection of any relevant IP, dissemination will be through publication in top international journals and domestic and international presentations. We will make sure that relevant IP is patented, potential licensees are recognised, and that possibilities for launching spin-outs are also properly identified.
General public: Appreciation and public support for scientific progress have underpinned technological progress in the UK ever since the practice of science became professionalised in the 19th century. We are committed to maintaining our side of this dialogue through explaining to the public what we do and why. One mechanism for this is press coverage of our research programme. The Nitschke group's 2009 Science paper generated a dozen stories in newspapers, TV, and radio across more than five countries, all with a positive bent. Another mechanism is structured outreach events; JRN will present his group's research to the 2014 international 'Pint of Science' festival (http://www.pintofscience.com/).
Education: In the context of undergraduate education, one of the Nitschke group's self-assembled systems will be highlighted in the next edition of a first-year undergraduate chemistry textbook and has already been adapted for use in undergraduate practical exercises.
Organisations
Publications
Privitera A
(2022)
Geminate and Nongeminate Pathways for Triplet Exciton Formation in Organic Solar Cells
in Advanced Energy Materials
Conaghan PJ
(2018)
Efficient Vacuum-Processed Light-Emitting Diodes Based on Carbene-Metal-Amides.
in Advanced materials (Deerfield Beach, Fla.)
Greenfield JL
(2021)
Electrically Induced Mixed Valence Increases the Conductivity of Copper Helical Metallopolymers.
in Advanced materials (Deerfield Beach, Fla.)
Yuan S
(2021)
Efficient and Spectrally Stable Blue Perovskite Light-Emitting Diodes Employing a Cationic p-Conjugated Polymer.
in Advanced materials (Deerfield Beach, Fla.)
Greenfield J
(2017)
Self-Assembly of Conjugated Metallopolymers with Tunable Length and Controlled Regiochemistry
in Angewandte Chemie
Greenfield JL
(2017)
Self-Assembly of Conjugated Metallopolymers with Tunable Length and Controlled Regiochemistry.
in Angewandte Chemie (International ed. in English)
Keyzer EN
(2018)
Post-Assembly Reactivity of N-Aryl Iminoboronates: Reversible Radical Coupling and Unusual B-N Dynamic Covalent Chemistry.
in Chemistry (Weinheim an der Bergstrasse, Germany)
Gillett A
(2022)
Controlling the Spin Exchange Energy through Charge Transfer for Triplet State Management in Organic Semiconductors
in Chemistry of Materials
Arefadib N
(2022)
Barriers and enablers to postpartum depression and anxiety screening: A qualitative study of Victorian maternal and child health nurses' practices.
in Health & social care in the community
Ronson T
(2017)
Design Principles for the Optimization of Guest Binding in Aromatic-Paneled Fe II 4 L 6 Cages
in Journal of the American Chemical Society
Freeman DME
(2017)
Synthesis and Exciton Dynamics of Donor-Orthogonal Acceptor Conjugated Polymers: Reducing the Singlet-Triplet Energy Gap.
in Journal of the American Chemical Society
Roberts DA
(2018)
Covalent Post-assembly Modification Triggers Multiple Structural Transformations of a Tetrazine-Edged Fe4L6 Tetrahedron.
in Journal of the American Chemical Society
Fallon KJ
(2019)
Exploiting Excited-State Aromaticity To Design Highly Stable Singlet Fission Materials.
in Journal of the American Chemical Society
McConnell AJ
(2017)
Subcomponent Exchange Transforms an FeII4L4 Cage from High- to Low-Spin, Switching Guest Release in a Two-Cage System.
in Journal of the American Chemical Society
Musser AJ
(2017)
Excitation Energy Delocalization and Transfer to Guests within MII4L6 Cage Frameworks.
in Journal of the American Chemical Society
Rizzuto FJ
(2017)
Tuning the Redox Properties of Fullerene Clusters within a Metal-Organic Capsule.
in Journal of the American Chemical Society
Greenfield JL
(2018)
Unraveling Mechanisms of Chiral Induction in Double-Helical Metallopolymers.
in Journal of the American Chemical Society
Ai X
(2018)
Efficient radical-based light-emitting diodes with doublet emission.
in Nature
Gillett AJ
(2021)
The role of charge recombination to triplet excitons in organic solar cells.
in Nature
Yong CK
(2017)
The entangled triplet pair state in acene and heteroacene materials.
in Nature communications
Schnedermann C
(2019)
A molecular movie of ultrafast singlet fission.
in Nature communications
Li F
(2022)
Singlet and triplet to doublet energy transfer: improving organic light-emitting diodes with radicals.
in Nature communications
Gillett AJ
(2021)
Spontaneous exciton dissociation enables spin state interconversion in delayed fluorescence organic semiconductors.
in Nature communications
Tang X
(2020)
Highly efficient luminescence from space-confined charge-transfer emitters
in Nature Materials
Guo H
(2019)
High stability and luminescence efficiency in donor-acceptor neutral radicals not following the Aufbau principle.
in Nature materials
Gillett AJ
(2022)
Dielectric control of reverse intersystem crossing in thermally activated delayed fluorescence emitters.
in Nature materials
Cui L
(2020)
Fast spin-flip enables efficient and stable organic electroluminescence from charge-transfer states
in Nature Photonics
Evans EW
(2018)
Vibrationally Assisted Intersystem Crossing in Benchmark Thermally Activated Delayed Fluorescence Molecules.
in The journal of physical chemistry letters
Gu Q
(2020)
Polymer Light Emitting Diodes with Doublet Emission.
in The journal of physical chemistry letters
Greenfield J
(2018)
Unraveling Mechanisms of Chiral Induction in Double-Helical Metallopolymers.
Schnedermann C
(2019)
A molecular movie of ultrafast singlet fission.
Description | New conjugated polymers have been prepared - several high-impact papers have been published, with more on the way. These polymers emit white light, and applications as conductive materials ('molecular wires') are being explored. We have also succeeded in controlling the left/right-handed helical twist of these polymers, which can control how these polymers may emit circularly polarized light. Such emission is relevant in the coming generation of new display applications (OLEDs). |
Exploitation Route | New conductive materials New sensors New light-emitting materials |
Sectors | Aerospace, Defence and Marine,Chemicals,Construction,Creative Economy,Digital/Communication/Information Technologies (including Software),Electronics,Energy,Environment,Healthcare,Manufacturing, including Industrial Biotechology,Pharmaceuticals and Medical Biotechnology,Security and Diplomacy |
URL | http://www-jrn.ch.cam.ac.uk |
Description | Jake Greenfield, one of the project's principals, was selected to present his work on this project at the STEM for Britain event in Parliament (http://www.setforbritain.org.uk/2017event.asp) on 13 March 2017. This competitive selection provided a greater depth of understanding of the fundamental problems addressed in this project to our nation's decision-makers. |
First Year Of Impact | 2017 |
Sector | Government, Democracy and Justice |
Impact Types | Societal |
Title | Research data supporting "Vibrationally Assisted Intersystem Crossing in Benchmark Thermally Activated Delayed Fluorescence Molecules" |
Description | Raw data for manuscript titled 'Vibrationally-assisted intersystem crossing in benchmark thermally activated delayed fluorescence molecules.' Data includes absorption and photoluminescence spectra for 2CzPN and 4CzIPN (Fig1b_Abs_2CzPN, Fig1b_Abs_4CzIPN, Fig1b_PL_2CzPN, Fig1b_PL_4CzIPN); transient electron spin resonance spectra for 2CzPN and 4CzIPN (Fig2c_2CzPN_0p4us, Fig2d_4CzIPN_0p4us); probability distributions for zero-field splitting in 2CzPN and 4CzIPN (Fig3a_2CzPN_ZFS_probability_distribution, Fig3b_4CzIPN_ZFS_probability_distribution); plots of zero-field splitting as a function of overlap index in 2CzPN and 4CzIPN (Fig3c_2CzPN_ZFS_overlap_idx, Fig3d_4CzIPN_ZFS_overlap_idx); and density plots (field versus time) of transient electron spin resonance spectra of 2CzPN and 4CzIPN (FigS1_TrESR_2CzPN_420nm_exc, FigS1_TrESR_4CzIPN_460nm_exc). |
Type Of Material | Database/Collection of data |
Year Produced | 2018 |
Provided To Others? | Yes |